KR960003798B1 - Catalyst for hydroformylation of olefin and its recovery method - Google Patents

Abstract

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Description

A method of converting aldehydes having one or two carbon atoms (manufacturing) through hydroformylation of an olefin using a hydrotalcite-type catalyst to which a water-soluble phosphine metal complex is immobilized, and the number of separations of the catalyst used (method) ) And Reuse Method

The present invention provides a method for preparing aldehydes having one or two carbon atoms from olefins and syngas using a solid catalyst in which a water-soluble complex compound is immobilized on a non-hydrotalcite-based solid support, and recovering and reusing a catalyst. It is about.

In the present invention, by using a solidified catalyst, it is possible to perform an effective hydroformylation reaction by taking advantage of easy handling of the catalyst in the hydroformylation reaction, and also in the field of separation recovery and reuse of the catalyst, a drastic improvement and advantages. To show you.

Conventionally, methods for producing aldehydes and alcohols by reacting olefins with carbon monoxide and hydrogen mixtures are already well known. Most important in this reaction, cobalt complexes are commercially used as catalysts. However, the use of rhodium complexes significantly increases the use of rhodium catalysts due to the advantages that the reaction temperature and reaction pressure can be lower than those of cobalt complexes. have. The use of homogeneous rhodium catalysts in the hydroformylation of olefins was described by Wilkinson [J. Chem. Soc. A. 2660, 1968, et al. Have been generalized by using organic phosphine ligands to increase the stability of catalysts and increase the linear aldehyde selectivity in aldehyde products. In the 1970s, "low pressure oxo processes" using rhodium phosphine catalysts were commercialized. Examples of technical developments in the field of hydroformylation reaction using rhodium and organic phosphines include organic phosphine compounds as ligands of rhodium complexes in hydroformylation reactions of cyclodienes in US Pat. A method of increasing the linear ratio of aldehyde by using 50 to 100 times with respect to rhodium has been published. U.S. Pat. The technique to make it is announced.

Low pressure oxo processes using homogeneous rhodium phosphine complex catalysts recover rhodium from the product to ameliorate it due to limited rhodium production, increased demand for rhodium in other fields and problems with higher prices, and difficulty in recovering rhodium from the product after the reaction. Various ways of doing this have been proposed. Useful techniques for the separation of catalytic metals related to hydroformylation include distillation of aldehydes from homogeneous catalyst reactants, formation of precipitates to enhance separation efficiency, extraction of metal complexes with suitable solvents, The method of adsorbing to a solid and separating is known.

However, due to the difficulty of the analytical and reprocessing processes, studies have been conducted to directly recover a catalyst through phase separation after the reaction by placing the catalyst in a different phase from the reactant or product. It can be classified into three types below.

1) a method in which a metal phosphine complex is supported on a solid and separated from the solution after centrifugation or using a filter;

2) a method of reusing the aqueous catalyst solution by dissolving the water-soluble metal phosphine complex in water and reacting in two phases, separating the reactant dissolved in the organic layer and the water-soluble rhodium phosphine complex dissolved in the water layer by a phase separation method,

3) A water-soluble rhodium phosphine complex is coated on the pore surface of the porous solid with a small amount of water so that the catalytic reaction occurs at the phase interface with the organic reactant. After the reaction, the porous solid containing the complex catalyst is separated from the reactant and reused. There is this.

In the method of 1), a method of immobilizing a metal compound by attaching phosphine to a polymer or inorganic solid by chemical method and coordinating a metal to phosphine is used. Rhodium phosphine complexes immobilized on the surface of polymers have a disadvantage of swelling due to organic solvents, organic reactants or products, and the relative coordination number of phosphine to metals is small. SIWoo, J. Mol. Catal. 61,27,1990] Metal phosphine complexes supported on inorganic solids also show similar disadvantages as those on polymer supported catalysts, and their application is also limited. Schwartz, J. Mol. Cat. 8,465, 1980

Method 2) uses a carboxylated or sulfonated phosphine to prepare a water-soluble metal complex by reacting this phosphine with a metal, dissolving it in a water layer to use as a catalyst solution, excess carboxylation or sulfonation Dissolved phosphine together to increase the stability of rhodium phosphine and linear selectivity of the reaction product. The oxo reaction process of propylene using this method has already been commercialized. However, the action of olefins having more than 3 carbon atoms has a low solubility in olefins in water, which limits their use. Examples of hydroformylation reactions using this method are shown in US Pat. No. 4,248,802 and CHEMTECH Sept. 570,1987.

The method of 3) is applicable to reactants or products which are not mixed with water, in particular, to olefins having 3 or more carbon atoms, so that the catalytic activity change due to the change in the catalyst water content is known to be very large. This increase in activity is believed to be due to an increase in interfacial surface area and the results of hydroformylation reactions related to this technique are published in J. Cat. 121,327, 1990.

The prior art hydroformylation of olefins related to the above catalyst separation reuse is based on a unique method and is partially satisfactory, but it is easier and more stable catalyst for improved catalyst production and reaction that eliminates these drawbacks. The demands and expectations for hydroformylation reaction techniques using manufacturing have always been present.

In the present invention, in the hydroformylation reaction of an olefin, a water-soluble metal phosphine complex is ion-exchanged to a hydrotalcite-type compound, which is a layered compound, by means of using a catalyst immobilized with a metal complex exhibiting an activity to be fixed between layers. Research and development of a method using a catalyst for the hydroformylation of olefins has been completed. As such a catalyst, the water-soluble phosphine complex immobilized on the hydrotalcite form material has a merit that a complex process is not required in the process of recovering and reusing the catalyst since the separation from the product after the reaction is simple. This method is characterized by using a catalyst on which a water-soluble metal complex exhibiting activity is supported on a solid support, unlike a conventional method using a catalyst prepared by immobilizing phosphine on a support and supporting a metal. Since the amount of negative charge of the water-soluble metal phosphine compound used is large, there is an effect of suppressing the elution of the complex from the support. In general, hydroformylation of olefins using water-soluble complex catalysts is known to proceed in two phases.However, the immobilization catalysts may be composed of three phases, that is, an organic layer, an aqueous layer, and a solid reaction system. It can promote catalysis.

The present invention is characterized by the advantages obtained by using an interlayer-fixed material in a hydrotalcite compound, in which a water-soluble metal phosphine complex is a layered compound, as a catalyst for hydroformylation of olefins, and the effective performance of this new reaction method. have. Catalytic material related to the present invention has the following general formula and chemical components.

Formula: T _t L ₁ SP _x -HT

T: Rh, Co or a combination thereof

L: Cl, CO, NO, COD, H, SR (R: alkyl group), phosphine or a combination thereof

SP: carboxylated or sulfonated phosphine

t: 1 ~ 2, 1: 0 ~ 8, x: 1 ~ 8 range

HT: [M (II) _1-x M (III) _x (OH) ₂ ] ^{x +} (Ax / n) yH ₂ O

here

M (II): Mg, Ni, Co, Zn, Cu or a combination thereof

M (III): Al, Cr, Fe or a combination thereof

A: organic or inorganic anion

x: composition ratio of M (III), 0.2 <x <0.4

n: charge amount of anion

y: number of water molecules

Catalytic materials having the general formula T _t L _l SP _x -HT are prepared in the form of hydrotalcite first, followed by the hydrotalcite, [M (II) _lx M (III) _x (OH) ₂ ] _{x +.} A water-soluble metal phosphine compound having a general formula of T _t L _l SP _x and a substance having a composition of (A _{x / n} ) yH ₂ O can be obtained by reacting in an aqueous solution, and rhodium of a T _t L _l SP _x -HT catalyst Alternatively, the weight ratio of cobalt may be made from a material in the range of about 1% to 15%, preferably in the range of 2% to 10%.

The hydroformylation reaction of olefins according to the present invention is carried out by bringing the synthesis gas and the olefin mixed reactant into contact with a T _t L _l SP _x -HT catalyst and the synthesis gas pressure is about 20 to 200 atm, preferably 40 to 150 atm. Atmospheric pressure, reaction temperature is in the range of about 50 ℃ to 200 ℃ preferably 80 ℃ to 150 ℃ range, the reaction time is carried out in the range of about 20 minutes to 48 hours, preferably 30 minutes to 24 hours and more preferably Synthesis gas ranges from 60 to 120 atm, reaction temperature from 100 ° C. to 120 ° C. and the preferred weight ratio of catalyst to olefin is in the range of 0.01% to 0.5% (up to about 1% if necessary). Applicable olefins are optionally taken as necessary in the range of C ₂ to C ₁₅ , preferably C ₃ to C ₁₂ and the liquid phase of the reactants is a liquid phase in which olefin, hexane, toluene, heptane, octane and combinations thereof or water is added It can consist only of liquid olefins which consist of or reactants. The above ranges for numerical values for pressure, temperature, and time are not intended to limit the present invention, but are presented as representative examples, and therefore, the above and below outside the range of the above angle value (s) are encompassed in the technical idea of the present invention. It is noted that the liquid phase of the reactants may be in any form, such as a liquid / phase mixture, if necessary, up to the gas phase or the solid phase.

The hydroformylation of olefins using a new immobilization catalyst is carried out by mixing the quantified solid catalyst with olefins distilled and purified under nitrogen atmosphere through a reactant inlet tube attached to a high pressure reactor, followed by synthesis gas filling and decompression process using a vacuum pump. The air inside the reactor was repeatedly removed 3-4 times, and then the reactor temperature was raised to the reaction temperature, and then the synthesis gas was charged at a predetermined pressure to proceed with the reaction for a predetermined time as mentioned above. After a certain time, the product was analyzed by gas chromatography after collecting through a sampling tube attached to the reactor. In this hydroformylation reaction, after completion of the reaction, the internal temperature of the high-pressure reactor is lowered to room temperature, the reaction product is removed from the reactor like a solid catalyst, and the liquid and the solid catalyst are separated using a filter and then the solid catalyst is extracted with hexane or other organic solvent. Can be washed and dried at room temperature and in the air for reuse.

The following examples are presented as representative example (s) to illustrate the performance of the present invention, and therefore the present invention is not limited to these Examples 1-5. The percent conversion used herein is the number of moles of converted olefins divided by the number of moles of olefins supplied and multiplied by 100 and the n / i ratio is the number of moles of normalaldehyde in the resulting aldehyde divided by the number of moles of isoaldehyde.

Example 1

About 70 g of 1-octene was mixed with about 0.2 g of Rh (H) (CO) (TPPTS) ₃ -HT (Mg _1-x Al _x ⁹ OH ₂ ) solidification catalyst powder and charged into a 300 ml high-pressure reactor. Syngas (CO + H ₂ ) and vacuum pump are used to remove the air in the reactor. The reaction is initiated by fixing the reactor internal temperature at about 100 ° C. (around) and introducing a synthesis gas of about 48 atmospheres (about) into the reactor. The solution inside the reactor is kept stirring to mix well with the solid catalyst. The conversion (yield) of 1-octene over time was analyzed by gas chromatography and the normal to isoaldehyde ratio was compared in Table 1. Where TPPTS is a triphenyltrisulfonated phosphine ligand and HT represents a substance in the form of hydrotalcite.

TABLE 1

Example 2

300 ml of a 70 g mixed solution (material obtained by the dimerization of butenes) with 0.25 g of Rh (H) (CO) (TPPTS) ₃ -HT (Mg _1-x Alx (OH) ₂ ) solidification catalyst powder After filling with a high pressure reactor of capacity, air in the reactor is removed by using a vacuum pump of syngas (CO + H ₂ ). The reaction is initiated by fixing the temperature inside the reactor at about 130 ° C. (around) and increasing the syngas pressure in the reactor to about 100 atm. After the settling time has elapsed, samples are taken from the reactor and analyzed and the reactor is cooled to room temperature. The reactant and the solid catalyst were separated using a filter paper, and the solid catalyst was used with about 50 ml of hexane. The solid catalyst is dried in air, and then 70 g of mixed octene and the recovered solid catalyst are mixed and placed in a reactor, followed by a hydroformylation reaction as described above. The catalyst reuse process was repeated seven times, and in the seventh use, 1-octene was used as the reaction olefin. The number of catalysts used, reaction conditions and reaction results are shown in Table 2.

TABLE 2

Example 3

Example using a Rh (H) (CO) (TPPTS) x-HT catalyst different from the catalyst used in Examples 1 and 2.

This catalyst was prepared by coordinating Rh ³⁺ to TPPTS by ion exchange of 9 times excess of TPPTS to hydrotalcite (Mg _0.75 Al _0.25 ratio) and reducing formaldehyde. 70 g of 1-octene and 0.2 g of Rh (H) (CO) (TPPTS) _x -HT catalyst were mixed and the reaction proceeded by the method in Example 1. Reaction conditions and reaction results are shown in Table 3.

TABLE 3

Example 4

70 g of 1-octene was mixed with 0.3 g of Co ₂ (CO) ₄ (TPPTS) ₂ -HT (Mg _lx Al _x (OH) ₂ ) solidification catalyst and charged into a 300 ml high-pressure reactor, followed by synthesis gas and vacuum. A pump is used to remove the air in the reactor. The reaction is initiated by fixing the temperature inside the reactor at about 130 ° C. (around) and introducing about 120 atmospheres of syngas into the reactor. The conversion rate of 1-octene over the reaction time was shown in Table 4 by gas chromatography.

TABLE 4

Example 5

70 g of 1-octene was mixed with 0.2 g of Rh ₂ (μ-SR) ₂ (CO) ₂ (TPPTS) ₂ -HT (R: tbutyl) solidification catalyst and charged into a 300 ml high-pressure reactor, followed by synthesis gas and vacuum pump. To remove the air in the reactor. The reaction is initiated by fixing the reactor internal temperature at about 103 ° C. (ambient) and about 110 ° C. (ambient) and introducing about 75 atmospheres of syngas into the reactor. The conversion of 1-octene over time was shown in Table 5 by gas chromatography analysis.

TABLE 5

Claims (6)

In the hydroformylation reaction of olefins using a substance represented by formula (I) in the form of hydrotalcite in which a water-soluble phosphine metal complex is immobilized, the reaction temperature is in the range of 50-200 ° C. A process for converting olefins having 1 to 2 carbon atoms to an olefin having a C _{3 to} C ₁₂ range. TtLl (SP) x-HT... … … … … … … … … … … … … … … … … … (Ⅰ) In the above formula, T: Rh, Co, or a combination thereof L: Cl, CO, NO, COD, H, SR (R: alkyl group), phosphine, or a combination thereof SP: carboxylated or sulfonated phosphine t: 1 ~ 2, 1: 0 ~ 8, x: 1 ~ 8 range HT: Hydrotalcite-type substance, its chemical composition is HT: [M (II) _1-x M (III) _x (OH) ₂ ] ^{x +} (Ax / n) yH ₂ O here M (II): Mg, Ni, Co, Zn, Cu or a combination thereof M (III): Al, Cr, Fe or a combination thereof A: organic or inorganic anion x: composition ratio of M (III), 0.2 <x <0.4 n: charge amount of anion y: number of water molecules The method of claim 1, wherein the water-soluble metal complex comprises a water-soluble rhodium phosphine compound and a water-soluble cobalt phosphine compound, and the water-soluble phosphine ligand uses a catalyst composed of triphenyltrisulfonated phosphine and triphenyltricarbonate phosphine. How to feature. The composition of claim 1, wherein the constituents of the hydrotalcite material [M (II) _2-x M (III) _x (OH) ₂ ] ^{x +} are Mg, Ni, Co, Zn or combinations thereof. , M (III) is characterized by using a catalyst which is Al, Cr, Fe or a combination thereof. The method of claim 1 wherein the olefin is in the range of C ₃ to C ₉ . A method of recovering and reusing a catalyst by separating the catalytic reaction mixture after the method of claim 1 by a filter and centrifugation. The method according to claim 1, wherein the reaction temperature is in the range of 80 to 150 ° C, and the synthesis gas pressure is in the range of 40 to 150 atmospheres.